Composite structures using interpenetrating polymer network adhesives

ABSTRACT

An interpenetrating polymer network (IPN) adhesive comprises an acrylated polymer system curable by radiation, and a flexible epoxy system thermally curable after the acrylated polymer system is cured.

TECHNICAL FIELD

This disclosure generally relates to composite structures, and dealsmore particularly with adhesives used in such composites.

BACKGROUND

Composite structures comprising parts that have different coefficientsof thermal expansion may induce residual stresses in the structureduring thermal curing or other fabrication processes that cause theparts to thermally expand at different rates. For example, and withoutlimitation, hybrid composite structures comprising a metal reinforcedwith carbon fiber polymers may be subject to thermal induced distortionwhile curing at elevated temperatures. In some cases, this problem maybe addressed by using fiber reinforced polymers that cure at roomtemperature, or which may be cured using various forms of radiation.However, room temperature cure polymers may have a short working life,long cure times, and require extra clean-up work. Room temperature curepolymers may also exhibit reduced performance characteristics comparedto polymers that are cured at elevated temperatures. Known radiationcured adhesives may be more brittle than desired and exhibit lower thandesired toughness, which may render these adhesives unsuitable for someapplications, particularly where resistance to impact loads is valued.

Interpenetrating polymer networks (IPN) have been used as an adhesive incomposite structures. IPNs are based on polymer systems that cure atdifferent temperatures using differing cure mechanisms, but may exhibitproperties that are superior to those of their constituent polymersystems. However, IPNs have not been adapted for solving the problem ofresidual stresses that are induced in composites by the differentialexpansion of the components of which the composite is formed.

Accordingly, there is a need for an IPN adhesive that may be used toreduce or eliminate residual stresses in composite structures that maybe caused by differential expansion of differing components used in thestructure, such as metals reinforced with carbon fiber polymers. Thereis also a need for a method of making composite structures that employIPN adhesives to reduce or eliminate the residual stresses.

SUMMARY

The disclosed embodiments provide an IPN adhesive that can be used tofabricate composite structures, and particularly hybrid structuresemploying both polymer resins and metals that may substantially reduceresidual stresses in the structure caused by differential thermalexpansion of the composite materials. The disclosed IPN adhesivecomprises two polymer adhesive systems that may be cured at differingtemperatures. One of the polymer systems may be cured at roomtemperature using a beam of radiation, such as an electron beam. Curingof the first polymer system at room temperature holds the compositeparts together so that they are fixed relative to each other as thestructure is being fully cured. Curing of the second polymer adhesive isachieved by thermal cycling at elevated temperatures. The second polymeradhesive, when cured, remains flexible which may renders the compositestructure more tolerant of impact loads, and less susceptible to barelyvisible impact damage (BVID).

In addition to increasing strength and durability, use of the disclosedIPN adhesive may result in weight savings by providing an effective wayto reinforce metal parts such as aluminum, and may reduce tooling costscomplexity while reducing process flow times.

According to one disclosed embodiment, a method is provided of bondingtwo parts together. The method comprises placing the parts together witha layer of IPN adhesive between the parts and attaching the parts toeach other by curing the first polymer system of the IPN adhesive usingradiation energy. The method further comprises thermally curing a secondflexible polymer system of the IPN adhesive after the first polymersystem has been cured. Curing the first adhesive system is performedsubstantially at room temperature using a beam of radiation, such as anelectron beam, and the second adhesive system is thermally cured at atemperature above room temperature. The first polymer system is cured toat least a stage which renders the part sufficiently rigid to allow thepart to be handled during subsequent processing steps. The first polymersystem may comprise an acrylated epoxy that forms a substantiallycontinuous structure when cured that attaches and holds the partstogether until the second polymer system is cured. The second polymersystem may be selected from the group consisting of a substantiallyflexible epoxy and a substantially flexible vinyl ester.

According to another disclosed embodiment, a method is provided offabricating a composite structure. The method comprises laying up firstand second composite laminates each having a fiber reinforced IPN matrixincluding a first polymer adhesive system, and a flexible second polymeradhesive system. The method further comprises curing the first polymeradhesive system and assembling the first and second laminates togetherwith a layer of the second polymer adhesive system therebetween. Themethod further comprises curing the second polymer adhesive system. Thefirst polymer adhesive system is cured substantially at room temperatureby a beam of radiation. The second polymer adhesive system is cured byco-curing the assembled laminates and the layer of adhesive during athermal cure cycle after the first polymer adhesive system has beencured.

According to still another embodiment, an IPN adhesive comprises anacrylated polymer system curable by radiation, and a flexible epoxysystem cured after the acrylated polymer system is cured. The acrylatedpolymer system may comprise an acrylated epoxy, and the radiation may beselected from the group consisting of an electron beam, ultravioletlight and x-ray radiation. The flexible polymer system may be oneselected from a group consisting of a flexible epoxy and a flexiblevinyl ester.

In accordance with another embodiment, a reinforced composite structureis provided. The composite structure comprises a reinforcement, and amatrix in which the reinforcement is embedded. The matrix includes anIPN forming a gradient interface around the reinforcement resulting inimproved shear force transfer from the matrix to the reinforcement. Thereinforcement may include fibers selected from the group consisting ofcarbon, fiberglass and an aramid. The IPN is a bi-continuous structureincluding an acrylated polymer and a flexible epoxy.

BRIEF DESCRIPTION OF THE ILLUSTRATIONS

FIG. 1 is an illustration of a functional block diagram of an IPNadhesive according to the disclosed embodiments.

FIG. 2 is an illustration of the IPN adhesive of FIG. 1, showing abi-continuous structure formed by dual polymer adhesive systems.

FIG. 3 is a sectional view of a hybrid composite structure, in which theparts are bonded together using the IPN adhesive.

FIG. 4 is an illustration of a flow diagram of a method of bonding twoparts of FIG. 3 together using the IPN adhesive.

FIG. 5 is an illustration of a sectional view of two co-cured compositelaminates joined together by a layer of the IPN adhesive.

FIG. 6 is an illustration of the area designated as FIG. 6 in FIG. 5.

FIG. 7 is an illustration of a flow diagram of a method of fabricatingthe composite structure shown in FIGS. 5 and 6.

FIG. 8 is an illustration of a fiber embedded in an IPN adhesive matrixin which a gradient interface has been formed around the fiber.

FIG. 9 is an illustration of a graphical plot useful in explaining thesynergy between the polymer systems used in the disclosed IPN adhesive.

FIG. 10 is a flow diagram of aircraft production and servicemethodology.

FIG. 11 is a block diagram of an aircraft.

DETAILED DESCRIPTION

Referring first to FIG. 1, the disclosed embodiments relate to afull-interpenetrating network (IPN) adhesive 16 which may be used as abonding adhesive or as a matrix in composite structures. The IPNadhesive 16 broadly comprises a first polymer system 18 and a second,flexible polymer system 20. The first polymer system 18 may be cured ator near room temperature using a beam (not shown) of radiation, such asan electron beam, however other forms of radiation including but notlimited to UV (ultra violet) and X-ray radiation may be employed. Thesecond polymer system 20 exhibits flexibility and toughness followingcuring, which is performed at elevated temperature during a suitablethermal cure cycle. As will be described below in more detail, the firstpolymer system 18 is cured at or near room temperature during thefabrication process to adhesively bond and effectively lock two or moreparts (not shown) together. The adhesive bond formed between the partsby the first polymer system 18 holds the parts in place and preventsthem from differentially expanding while the second polymer system 20 isthermally curing. Locking the parts together in this manner may reduceor eliminate the possibility of distortion of the parts during thefabrication process. The flexible second polymer system 20 provides thebond with both flexibility and toughness.

The first polymer system 18 may comprise an acrylated polymer such asacrylated epoxy. For example and without limitation, the acrylated epoxymay comprise one of bisphenol A diacrylate (BPADA) with a trifunctionalacrylate, and trimethylolpropane triacrylate (TMPTA) cross-linkingagent. The second flexible polymer system 20 may be one selected fromthe group consisting of flexible epoxies and vinyl esters. For exampleand without limitation, the second flexible polymer system may be one ofBis(3,4-EpoxyCyclohexylmethyl) Adipate (BECA) and the combination of aDiglycidyl ether of bisphenol A (DGEBA) with a Polypropylene GlycolDiglycidyl Ether (PPGDE) chain extender with an imidazole such as2-Ethyl 4-Methylimidazole (EMI) or an anhydride as the curing catalyst.

Although not shown in the Figures, the second flexible polymer system 20may include a suitable thermal cure initiator, such as, withoutlimitation, imidazole or anhydride for cross linking the second polymersystem 20. In one practical embodiment, the IPN adhesive 16 comprisesapproximately 67% acrylate and 33% flexible epoxy (including the curingagent). In another practical embodiment, the IPN adhesive 16 comprisesapproximately 40% acrylate, and approximately 60% flexible epoxy.

FIG. 2 illustrates the IPN adhesive 16 in a fully cured state in whichthe two polymer systems 18, 20 respectively form bi-continuousstructural networks 22, 24 that are intertwined to form what issometimes referred to as a double gyroidal structure. The structuralnetwork 22 formed by the first polymer system 18 may function as arelatively high strength adhesive to bond parts together, but which mayexhibit some degree of brittleness. The second structural network 24formed by the second polymer system 20 is relatively flexible, providingthe IPN adhesive 16 with resistance to impact loading.

FIG. 3 illustrates a hybrid composite structure 25 comprising two parts26, 28 which may respectively comprise for example and withoutlimitation, a composite laminate, and a metal. The two parts 26, 28 maybe bonded together using a layer 27 of the IPN adhesive 16. Referringalso now to FIG. 4, the hybrid composite structure 25 may be fabricatedby a method that begins at step 30 in which the parts 26, 28 are placedtogether with the layer 27 of the IPN adhesive 16 therebetween.

Next, at step 32, the parts 26, 28 are bonded together by curing thefirst polymer system 18 (FIG. 1) using a beam 45 of radiation (FIG. 5)that is directed onto the structure 25 from a suitable radiation source47. The curing process performed at step 32 may be carried out at ornear room temperature, consequently the parts 26, 28 are initiallybonded together without differential expansion that may be caused bycuring at elevated temperatures. Finally, at step 34, the second polymersystem 20 is thermally cured by subjecting the assembled compositestructure 25 to a thermal cure cycle at elevated temperatures. Duringthis thermal curing, differential thermal expansion of the parts 26, 28is substantially reduced or eliminated due to the fact that the parts26, 28 have already been bonded together, and thus are fixed relative toeach other by the first polymer system.

FIGS. 5 and 6 illustrate another application of the IPN adhesive 16(FIG. 1). In this example, two multi-ply, fiber reinforced laminates 36,38 are joined together by a layer 40 of a flexible polymer adhesive suchas a flexible epoxy to form a composite structure 35. As shown in FIG.6, each of the laminates 36, 38 comprises a fiber reinforcement 41 heldand embedded in a matrix comprising the IPN adhesive 16 describedpreviously. Thus, each of the laminates 36, 38 comprises bi-continuousfirst and second polymer systems 18, 20 as described above in connectionwith FIGS. 1 and 2, while the layer 40 comprises a thermally curable,flexible polymer such as a flexible epoxy which may be substantially thesame as the second, flexible polymer system 20 forming part of the IPNadhesive matrix 16. As will be discussed below, when the compositestructure 35 is fully cured, the flexible polymer system 20 (FIG. 1)extends continuously from one laminate 36 through bond layer 40 to theother laminate 38.

FIG. 7 illustrates a method of fabricating the composite structure 35shown in FIGS. 5 and 6. Beginning at 44, first and second laminates 36,38 are formed by laying up plies (not shown) of prepreg (not shown)using conventional processes and tooling suitable for the application.IPN adhesive 16 comprising the two unreacted, bi-continuous polymersystems 18, 20 (FIG. 1) is used as the ply matrix into which the fiberreinforcement 41 is embedded. Next, at step 46, each of the laminates36, 38 is cured to at least a stage that allows the laminates to behandled by directing a beam 45 of radiation produced by a suitableradiation source 47 onto each of the laminates 36, 38. The radiationbeam 45 may comprise an electron beam (EB), a UV beam or a beam ofX-rays. This radiation beam curing, which may be carried out at or nearroom temperature, results in curing of the first polymer system 18 whichforms one component of the ply matrix, and cross linking, shown by thenumeral 42 in FIG. 6, of the first polymer system 18.

At this point, the second polymer system 20 remains unreacted, howeverthe curing of the first polymer system 18 stiffens the laminate 36, 38to at least a stage allowing them to be handled as necessary for furtherprocessing. In fact, the following the room temperature curing, thelaminates 36, 38 may have nearly as much rigidity as fully curedlaminates, consequently, when placed together under pressure in tooling(not shown), the laminates 36, 38 may exhibit little or no deformation.At step 48, the laminates 36, 38 are assembled together using a bondlayer 40 of a flexible, thermally curable polymer that may besubstantially the same as that comprising the second, flexible polymersystem 20 forming part of the IPN adhesive 16. With the laminates 36, 38having been assembled, then at step 50, the second polymer system 20along with the bond layer 40 are co-cured by subjecting the assembledlaminates 36, 38 to a thermal cure cycle. It should be noted here thatwhen imidazol is used as a curing agent, it results in a 2-step curingprocess. The first step is an epoxy adduct stage where the imidazolemolecules simply attach themselves to the ends of epoxy molecules; thisoccurs at approximately 60 degrees C. and results in a significantincrease in viscosity. The second step to the curing process iscross-linking of epoxies and epoxy adducts which occurs at approximately160 degrees C.

FIG. 8 illustrates the use of the previously described IPN adhesive 16as a matrix for holding a reinforcement 54 which may comprise fibers,beads, particles or other reinforcing media. As in previous examples,the IPN adhesive 16 comprises first and second polymer systems 18, 20(FIG. 1) which are respectively curable at differing temperatures. Thesecond polymer system 20 (FIG. 1) which may comprise a flexible epoxy,has a higher surface tension than the first polymer system 18 which maycomprise an acrylated epoxy. This higher surface tension causes theflexible second polymer system 20 to preferentially attach to thereinforcement 54, resulting in a gradient interface 56 around thereinforcement 54 that is somewhat flexible. The flexibility provided bythe gradient layer 56 is advantageous in that it may assist in bettertransferring shear forces from the reinforcement 54 to the IPN adhesivematrix 16. Also, the gradient layer 56 may aid in establishing animproved bond between the IPN adhesive matrix 16 and the reinforcement54. For example, where the IPN adhesive matrix 16 includes an acrylatethat may not bond well to reinforcement 54 that is a carbon fiber, theflexible material forming the gradient layer 56 may improve the bondbetween the adhesive matrix 16 and the carbon fiber 54.

Use of the IPN 16 resulting in the formation of the gradient layer 56may be advantageously employed in fabricating filament wound products(not shown). At the conclusion of wet filament winding or an RTM (resintransfer molding) process, an electron beam head (not shown) can beswept over the part to provide the initial cure. The entire structurewill be dimensionally locked by this room temperature curing step, whichmay avoid the need for expensive tooling or autoclaves for the secondarythermal cure cycle.

Attention is now directed to FIG. 9 which is a stress-strain performanceplot that illustrates the synergy provided by the systems 18, 20 formingthe disclosed IPN adhesive 16. Curve 62 shows the performance of aflexible epoxy comprising a 50/50 mixture of two typical flexible epoxycomponents, while curve 64 shows the performance of a typical acrylatethat includes 20% a content of a trifunctional acrylate. Curve 66represents the performance of the disclosed IPN adhesive 16, which inthis example, comprises a 50/50 combination of the flexible epoxymixture represented by curve 62 and the acrylate mixture represented bycurve 64.

Rather than lying half way between the curves, 62, 64, as might benormally expected, the performance of the dual system IPN 16 shown bycurve 66 indicates that the IPN 16 has a modulus that approaches that ofthe stiffer acrylate (curve 64), and an elongation that approaches thatof the flexible epoxy (curve 62). Thus, the first polymer system 18(FIG. 1) provides the strength necessary for holding parts together butmay have limited ability to deform upon an impact load, while theflexible second polymer system 20 provides the IPN 20 with theflexibility required to withstand impact loads. The second flexiblepolymer system 20 effectively allows the first polymer system 18 to movearound and flex.

Referring next to FIGS. 10 and 11, embodiments of the disclosure may beused in the context of an aircraft manufacturing and service method 68as shown in FIG. 10 and an aircraft 70 as shown in FIG. 11. Duringpre-production, exemplary method 68 may include specification and design72 of the aircraft 70 and material procurement 74. During production,component and subassembly manufacturing 76 and system integration 78 ofthe aircraft 70 takes place. The disclosed IPN adhesive 16 may be usedto assemble parts and subassemblies as part of the manufacturing processstep 76. Thereafter, the aircraft 70 may go through certification anddelivery 80 in order to be placed in service 82. While in service by acustomer, the aircraft 70 may be scheduled for routine maintenance andservice 166 (which may also include modification, reconfiguration,refurbishment, and so on), in which the IPN adhesive 16 may be used torepair or refurbish parts and assemblies.

Each of the processes of method 68 may be performed or carried out by asystem integrator, a third party, and/or an operator (e.g., a customer).For the purposes of this description, a system integrator may includewithout limitation any number of aircraft manufacturers and major-systemsubcontractors; a third party may include without limitation any numberof vendors, subcontractors, and suppliers; and an operator may be anairline, leasing company, military entity, service organization, and soon.

As shown in FIG. 11, the aircraft 70 produced by exemplary method 68 mayinclude an airframe 86 with a plurality of systems 88 and an interior90. Examples of high-level systems 88 include one or more of apropulsion system 92, an electrical system 94, a hydraulic system 96,and an environmental system 98. Any number of other systems may beincluded. The disclosed IPN adhesive 16 may be used to fabricate partsused in the airframe 86 and in the interior 90. Although an aerospaceexample is shown, the principles of the invention may be applied toother industries, such as the automotive industry.

The apparatus embodied herein may be employed during any one or more ofthe stages of the method 68. For example, components or subassembliescorresponding to production process 78 may be fabricated or manufacturedin a manner similar to components or subassemblies produced while theaircraft 70 is in service. Also, one or more apparatus embodiments maybe utilized during the production stages 76 and 78, for example, bysubstantially expediting assembly of or reducing the cost of an aircraft152. Similarly, one or more apparatus embodiments may be utilized whilethe aircraft 68 is in service, for example and without limitation, tomaintenance and service 84.

Although the embodiments of this disclosure have been described withrespect to certain exemplary embodiments, it is to be understood thatthe specific embodiments are for purposes of illustration and notlimitation, as other variations will occur to those of skill in the art.

What is claimed:
 1. A method of bonding two parts together, comprising:placing the parts together with a layer of an interpenetrating polymernetwork (IPN) adhesive between the parts; attaching the parts to eachother by curing a first polymer system of the IPN adhesive usingradiation energy; and thermally curing a second flexible polymer systemof the IPN adhesive after the first polymer system has been cured. 2.The method of claim 1, wherein: curing the first adhesive system isperformed substantially at room temperature using a beam of theradiation energy, and thermally curing the second adhesive system isperformed at a temperature above room temperature.
 3. The method ofclaim 1, wherein the first polymer system is cured to a stage thatallows handling of the parts.
 4. The method of claim 1, wherein thefirst polymer system is an acrylated epoxy forming a first substantiallycontinuous structure when cured that attaches and holds the partstogether until the second polymer system is cured.
 5. The method ofclaim 1, wherein the second polymer system is selected from the groupconsisting of: a substantially flexible epoxy, and a substantiallyflexible vinyl ester.
 6. The method of claim 1, wherein the parts haverespectively different coefficients of thermal expansion.
 7. The methodof claim 1, wherein one of the parts is a fiber reinforced composite andthe other of the parts includes metal.
 8. Parts bonded together by themethod of claim
 1. 9. A method of fabricating a composite structure,comprising: laying up first and second composite laminates each having afiber reinforced interpenetrating polymer network (IPN) matrix includinga first polymer adhesive system and a flexible second polymer adhesivesystem; curing the first polymer adhesive system; assembling the firstand second laminates together with a layer of the second polymeradhesive system therebetween; and curing the second polymer adhesivesystem.
 10. The method of claim 9, wherein curing the first polymeradhesive system is performed at substantially room temperature by a beamof radiation.
 11. The method of claim 10, wherein curing the secondpolymer adhesive system is performed by co-curing the assembledlaminates and the layer of adhesive during a thermal cure cycle afterthe first polymer adhesive system has been cured.
 12. The method ofclaim 9, wherein curing of the first polymer adhesive system isperformed before the first and second laminates are assembled togetherand provides the laminates with sufficient rigidity to allow handling ofthe laminates.
 13. The method of claim 9, wherein the curing of thesecond polymer adhesive system produces a substantially continuousflexible polymer structure extending through the first and secondlaminates and the bond.
 14. A composite structure fabricated by themethod of claim
 9. 15. An interpenetrating polymer network (IPN)adhesive, comprising: an acrylated polymer system curable by radiation;and a flexible epoxy system thermally curable after the acrylatedpolymer system is cured.
 16. The IPN adhesive of claim 15, wherein theacrylated polymer system is an acrylated epoxy.
 17. The IPN adhesive ofclaim 16, wherein the acrylated epoxy is curable by radiation selectedfrom the group consisting of an electron beam, ultraviolet light andx-rays.
 18. The IPN adhesive of claim 15, wherein the flexible polymersystem is one selected from the group consisting of: a flexible epoxy,and a flexible vinyl ester.
 19. The IPN adhesive of claim 16, whereinthe acrylated epoxy includes at least one of: bisphenol, a diacrylate(BPADA) with A trifunctional acrylate, trimethylolpropane, and atriacrylate (TMPTA) cross-linking agent.
 20. The IPN adhesive of claim16, wherein the flexible epoxy system is selected from the groupconsisting of: Bis(3,4-EpoxyCyclohexylmethyl) Adipate (BECA), and acombination of a Diglycidyl ether of bisphenol A (DGEBA) with aPolypropylene Glycol Diglycidyl Ether (PPGDE) chain extender.
 21. TheIPN adhesive of claim 15, wherein the flexible polymer system includes athermal cure initiator.
 22. A reinforced composite structure,comprising: a reinforcement; and a matrix in which the reinforcement isembedded, the matrix including an interpenetrating polymer network (IPN)forming a gradient interface around the reinforcement resulting inimproved shear force transfer from the matrix to the reinforcement. 23.The reinforced composite structure of claim 22, wherein: the IPN is abi-continuous structure including an acrylated polymer and a flexibleepoxy, and the reinforcement includes fibers selected from the groupconsisting of carbon, fiberglass and an aramid.
 24. A method of bondingmetal and composite parts together, comprising: placing the partstogether with a layer of an interpenetrating polymer network (IPN)adhesive between the parts; attaching the parts to each other by curinga first polymer system of the IPN adhesive at room temperature using anelectron beam of radiant energy until the parts have sufficient rigidityto be handled, wherein the first polymer system is an acrylated epoxyforming a first substantially continuous structure when cured thatattaches and locks the parts together until the second polymer system iscured; and thermally curing a second flexible polymer system of the IPNadhesive after the first polymer system has been cured using a thermalcure cycle above room temperature, wherein the second polymer system isselected from the group consisting of a substantially flexible epoxy,and a substantially flexible vinyl ester.
 25. An interpenetratingpolymer network (IPN) adhesive, comprising: an acrylated epoxy systemcurable by radiation selected from the group consisting of an electronbeam, ultraviolet light and x-rays, wherein the acrylated epoxy systemincludes at least one of— bisphenol, a diacrylate (BPADA) with Atrifunctional acrylate, trimethylolpropane, and a triacrylate (TMPTA)cross-linking agent; and a flexible epoxy system thermally curable afterthe acrylated epoxy system is cured, wherein the flexible epoxy systemincludes a thermal cure initiator and is selected from the groupconsisting of Bis(3,4-EpoxyCyclohexylmethyl) Adipate (BECA), and acombination of a Diglycidyl ether of bisphenol A (DGEBA) with aPolypropylene Glycol Diglycidyl Ether (PPGDE) chain extender.